The electrochemical reduction of carbon dioxide (CO2) powered by renewable energy is an attractive sustainable approach to mitigate CO2 emissions and to produce fuels or value-added chemicals. In order to tackle the challenges related to selectivity, activity, overpotential and durability, transition metal-based catalysts have been widely investigated in the last decades. In an effort to bridge the gap between the fields of homogeneous and heterogeneous catalysis, this review aims to survey the main strategies explored for the rational design of a wide variety of different metal catalysts, ranging from molecular systems to single-atom and nanostructured catalysts. Transition metal complexes containing heme and non-heme ligands have been selected to discuss the recent advances in the understanding of the structure–function relationship in molecular homogeneous catalysis as well as to summarize the main approaches proposed for the heterogenization or confinement of molecular catalysts on conductive surfaces. The main strategies to minimize catalyst cost are also presented, leading to atomically dispersed molecular-like M–Nx moieties embedded on 2D conducting materials. The superior performances of single-atom catalysts (SACs) and the structural similarity with their molecular analogs, suggest that transition metal catalysts containing well-defined sites may be intrinsically more active and selective towards CO2 conversion than the bulk heterogeneous materials. Finally, design approaches for metal nanoparticles (NPs) based on size, shape, and support tuning are summarized and compared to novel strategies based on the interaction with surface-bonded organic molecules. The studies herein presented show that the basic principles in molecular catalysis and organometallic chemistry can be effectively used to design new efficient and selective heterogeneous catalysts for CO2 reduction.

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Transition metal-based catalysts for the electrochemical CO2 reduction: from atoms and molecules to nanostructured materials

The electrocatalytic transformation of carbon dioxide has been a topic of interest in the field of CO2 utilization for a long time. Recently, the area has seen increasing dynamics as an alternative strategy to catalytic hydrogenation for CO2 reduction. While many studies focus on the direct electron transfer to the CO2 molecule at the electrode material, molecular transition metal complexes in solution offer the possibility to act as catalysts for the electron transfer. C1 compounds such as carbon monoxide, formate, and methanol are often targeted as the main products, but more elaborate transformations are also possible within the coordination sphere of the metal center. This perspective article will cover selected examples to illustrate and categorize the currently favored mechanisms for the electrochemically induced transformation of CO2 promoted by homogeneous transition metal complexes. The insights will be corroborated with the concepts and elementary steps of organometallic catalysis to derive potential strategies to broaden the molecular diversity of possible products.

Transition Metal Complexes as Catalysts for the Electroconversion of CO 2 : An Organometallic Perspective

Unveiling the promotion of accelerated water dissociation kinetics on the hydrogen evolution catalysis of NiMoO4 nanorods

Electrochemical CO2 reduction (ECR) to value-added chemicals and fuels is regarded as an effective strategy to mitigate climate change caused by CO2 from excess consumption of fossil fuels. To achieve CO2 conversion with high faradaic efficiency, low overpotential, and excellent product selectivity, rational design and synthesis of efficient electrocatalysts is of significant importance, which dominates the development of ECR field. Individual organic molecules or inorganic catalysts have encountered a bottleneck in performance improvement owing to their intrinsic shortcomings. Very recently, organic-inorganic hybrid nanomaterials as electrocatalysts have exhibited high performance and interesting reaction processes for ECR due to the integration of the advantages of both heterogeneous and homogeneous catalytic processes, attracting widespread interest. In this work, the recent advances in designing various organic-inorganic hybrid nanomaterials at the atomic and molecular level for ECR are systematically summarized. Particularly, the reaction mechanism and structure-performance relationship of organic-inorganic hybrid nanomaterials toward ECR are discussed in detail. Finally, the challenges and opportunities toward controlled synthesis of advanced electrocatalysts are proposed for paving the development of the ECR field.

Organic–Inorganic Hybrid Nanomaterials for Electrocatalytic CO2 Reduction

Developing effective, stable, and economical electrocatalysts to achieve highly efficient overall water splitting under a large current density in industries is critical for renewable H2 production...

In Situ-Grown Cobalt–Iron Phosphide-Based Integrated Electrode for Long-Term Water Splitting under a Large Current Density at the Industrial Electrolysis Temperature

Herein, we have synthesized fluorine-doped cobalt molybdate (F-CoMoO4) nanosheet arrays on graphite felt (GF) to efficiently promote the oxygen evolution reaction (OER) kinetics. Experimental results show that F-CoMoO4 has two significant effects: 1) inducing rich oxygen vacancies, and 2) optimizing the electronic configuration of CoMoO4, which is beneficial for exposure of active sites. The as-obtained F-CoMoO4-x-2@GF electrocatalyst exhibits lower OER overpotential of 256 mV at 10 mA cm−2 with a small Tafel slope of 64.4 mV dec−1 in alkaline solution, resulting in a nearly 100 mV of OER catalytic activity enhancement compared with that of pure CoMoO4. DFT results reveal that the change of Mo 4d state reduces the band-gap and increases the electrical conductivity of CoMoO4, thus optimizing its intrinsic activity. The synthesis strategy used in this work may provide some ideas for enhancing the electrical conductivity of other transition metal oxides (TMOs).

Novel fluorine-doped cobalt molybdate nanosheets with enriched oxygen-vacancies for improved oxygen evolution reaction activity

Transition metal oxides (TMOs) have acquired much attention on account of their abundant reserves and variable components, but sluggish charge transfer rate, limited electrochemically active sites,...

Weiwei Xie

Papers

Novel fluorine-doped cobalt molybdate nanosheets with enriched oxygen-vacancies for improved oxygen evolution reaction activity

Self-Supporting Clusters Constituted of Nitrogen-DopedCoMoO 4 Nanosheets for Efficiently Catalyzing the HydrogenEvolution Reaction in Alkaline Media

How does the ligands structure surrounding metal-N4 of Co-based macrocyclic compounds affect electrochemical reduction of CO2 performance?